Polymeric Plasticizer Compositions

ABSTRACT

The present invention relates to polymeric plasticizer compositions made from an aromatic acid source, a glycol, and a C 4 -C 36  monocarboxylic acid, or ester or anhydride thereof. The aromatic acid source can include polymeric materials such as recycled polyethylene terephthalate (PET). The present invention also relates to methods for making the polymeric plasticizer compositions, to methods of plasticizing polymeric materials, and to plasticized polymeric compositions. The polymeric plasticizers are useful for plasticizing various polymers, such as thermoplastic polymers, including, for example, polyvinyl chloride (PVC). The polymeric plasticizers provide a sustainable alternative to conventional phthalate ester plasticizers, such as diisooctyl phthalate (DOP).

RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationSer. No. 62/072,074 filed on Oct. 29, 2014 and U.S. Provisional PatentApplication Ser. No. 62/099,930 filed on Jan. 5, 2015, the disclosuresof each of which are incorporated by reference herein in their entirety.

FIELD OF THE INVENTION

The present invention relates to polymeric plasticizer compositions madefrom an aromatic acid source, a glycol, and a C₄-C₃₆ monocarboxylicacid, or ester or anhydride thereof. The aromatic acid source caninclude polymeric materials such as recycled polyethylene terephthalate(PET). The present invention also relates to methods for making thepolymeric plasticizer compositions, to methods of plasticizing polymericmaterials, and to plasticized polymeric compositions. The polymericplasticizers are useful for plasticizing various polymers, such asthermoplastic polymers, including, for example, polyvinyl chloride(PVC). The polymeric plasticizers provide a sustainable alternative toconventional phthalate ester plasticizers, such as diisooctyl phthalate(DOP).

BACKGROUND OF THE INVENTION

Plasticizers are additives used to increase the plasticity or fluidityof materials. Examples of materials that are commonly plasticizedinclude plastics, clays, and concrete. With respect to polymericmaterials such as plastics, it has been hypothesized that plasticizersperform their plasticizing function by embedding between the polymerchains, thus spacing them out and increasing the free volume for thepolymer. This increase in the free volume results in a lowering of theglass transition temperature (T_(g)) for the polymer, thus rendering itmore flexible or malleable, in other words, rendering it more plastic.

An important application of plasticizers is for plasticizing polymericmaterials, particularly polyvinyl chloride (PVC). By some estimates,over 90% of the plasticizer market is directed to plasticizing PVC. See,David F. Cadogan and Christopher J. Howick “Plasticizers” in Ullmann'sEncyclopedia of Industrial Chemistry 2000, Wiley-VCH, Weinheim. Withoutthe addition of a plasticizer, PVC is a rigid material. PVC can be madesofter and more flexible by the addition of plasticizers. PlasticizedPVC is used as a replacement for rubber, and has applications in manyareas including, for example, pneumatic tires, electrical wire and cableinsulation, flooring, coatings, tubing, inflatable products, toys,foams, roofing membranes, food packaging, footwear, coats, sportinggear, magnetic cards, hoses, furniture, exterior siding, bottles,inflatable products, examination gloves, flexible sheeting, gaskets,medical devices, containers, and imitation leather.

The most common plasticizers used for plasticizing PVC and otherpolymers are esters of polycarboxylic acids with linear or branchedchain aliphatic alcohols. Examples of these carboxylic acids arephthalic acid and trimellitic acid. Examples of the aliphatic alcoholsused to esterify these acids include C₆ to C₁₀ alcohols. One of the morewidely used plasticizers is diisoctyl phthalate (DIOP or DOP), which isalso known by a number of other names including dioctyl phthalate,diethylhexyl phthalate (DEHP), di-2-ethylhexyl phthalate, andbis-2-ethylhexylphthalate.

Despite their utility, plasticizers are not always fully compatible withand leach out of and evaporate from the polymers they are intended toplasticize. For example, it is believed that plasticizers that haveleached out of and vaporized from the plastic interior of a carcontribute to the characteristic new car smell. The loss of plasticizerfrom a polymeric material can have negative consequences. Firstly, asthe plasticizer is lost from the polymeric material, the surface of thepolymer can become sticky or tacky. In some instances the polymericmaterial releases droplets of plasticizer on its surface. In otherwords, the polymeric material sweats or weeps. As the plasticizer iscontinuously lost, the polymeric material can eventually become morerigid and brittle. Thus the desired flexibility characteristics of thepolymeric material are lost and the material can fail. Secondly, thereare potential health concerns if consumers come in contact with theleached or vaporized plasticizer materials, such as through physicalcontact or via inhalation or ingestion. Additionally, there arepotential environmental concerns due to the leached or vaporizedplasticizers being released into the environment. Because of theseconcerns, there have been movements to limit or ban commonly usedplasticizers such as DOP in some countries.

Separate from these safety and environmental concerns with plasticizers,there is an overarching question of sustainability and environmentalstewardship in the production and use of products. It would be highlydesirable to develop plasticizers that can be prepared from sourcesother than nonrenewable petrochemical feedstocks. Furthermore, it wouldbe desirable to develop plasticizers that can be prepared by recyclingwaste streams. The safe disposal or reuse of waste materials fromvarious sources is an environmental and economic challenge. Such wasteshad typically gone into landfills, but as landfill capacity is becomingever scarcer and disposal costs are continuously increasing, costeffective and environmentally acceptable alternatives are needed to dealwith these waste materials. For example, a readily available wastestream is produced from waste thermoplastic polyesters, including wastepolyethylene terephthalate (PET) streams (e.g., from plastic beveragecontainers). Therefore, it would be advantageous to find ways to recyclesuch waste streams into new products.

Regarding the plasticizers themselves, there are the challenges ofdeveloping materials having optimal physical and chemical properties.For example, plasticizers that are compatible with and useful forplasticizing PVC should have low acid values, low hydroxyl values, lowoxygen ether content, moderate to high molecular weights (in the case ofpolymeric plasticizers), and viscosities that allow reasonableprocessing to make plasticized polymeric materials. Plasticizers notmeeting the criteria for acid and hydroxyl values can be detrimental tothe PVC, causing water uptake of the polymer and more serious issuessuch as dehydrohalogenation, resulting in acid release, failure of thepolymer, and potential damage to materials in contact with the failingpolymer. Additionally, the plasticizers should be safe for use inconsumer products and not detrimental to the environment. Thesephysical, chemical, safety, and environmental criteria raise difficulttechnical challenges for developing new plasticizers.

In addition to these forgoing challenges are the technical and economicchallenges to cost effectively produce and formulate the plasticizers.

In many instances, it would be highly desirable to have improvedplasticizers. It is apparent there is an ongoing need to develop newplasticizers that are compatible with and have the desired technical andperformance characteristics for plasticizing polymeric materials such asPVC. It is important that these plasticizers do not easily leach orevaporate from the plasticized polymer and do not have untoward healthor environmental concerns. These plasticizers should be technically andeconomically viable to produce. Furthermore, it would be highlyadvantageous to develop plasticizers that can be sourced fromsustainable sources to employ and reduce waste streams.

We surprisingly found that polymeric plasticizer compositions meetingthe foregoing criteria can be made from an aromatic acid source, aglycol, and a component selected from a C₄-C₃₆ monocarboxylic acid, orester or anhydride thereof or further comprising a C₄-C₃₆ alcohol.

SUMMARY OF THE INVENTION

The present invention relates to polymeric plasticizer compositions madefrom an aromatic acid source, a glycol, and a C₄-C₃₆ monocarboxylicacid, or ester or anhydride thereof. The aromatic acid source caninclude polymeric materials such as recycled polyethylene terephthalate(PET). The present invention also relates to methods for making thepolymeric plasticizer compositions, to methods of plasticizing polymericmaterials, and to plasticized polymeric compositions. The polymericplasticizers are useful for plasticizing various polymers, such asthermoplastic polymers, including, for example, polyvinyl chloride(PVC). The polymeric plasticizers provide a sustainable alternative toconventional phthalate ester plasticizers, such as diisooctyl phthalate(DOP).

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a polymeric plasticizer compositioncomprising a reaction product of: (a) an aromatic acid source selectedfrom an aromatic diacid, an aromatic diacid anhydride, an aromaticdiacid monoester, an aromatic diacid diester, an aromatic linear esteroligomer, an aromatic linear thermoplastic polyester, and combinationsthereof; (b) a glycol; and (c) a C₄-C₃₆ monocarboxylic acid, ester oranhydride thereof.

In one aspect the present invention relates to a polymeric plasticizercomposition comprising recurring units derived from: (a) an aromaticacid source selected from an aromatic diacid, an aromatic diacidanhydride, an aromatic diacid monoester, an aromatic diacid diester, anaromatic linear ester oligomer, an aromatic linear thermoplasticpolyester, and combinations thereof; (b) a glycol; and (c) a C₄-C₃₆monocarboxylic acid, ester or anhydride thereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein the C₄-C₃₆ monocarboxylic acid, ester oranhydride thereof is a chain terminator.

In another aspect the present invention relates to a polymericplasticizer composition wherein the C₄-C₃₆ monocarboxylic acid, ester oranhydride thereof is further substituted with one or more carbonylgroups.

In another aspect the present invention relates to a polymericplasticizer composition having a number average molecular weight from500 to 25,000 grams/mole.

In another aspect the present invention relates to a polymericplasticizer composition having a number average molecular weight from800 to 10,000 grams/mole.

In another aspect the present invention relates to a polymericplasticizer composition having a number average molecular weight from1000 to 8000 grams/mole.

In another aspect the present invention relates to a polymericplasticizer composition having an acid value less than 10 mg KOH/g.

In another aspect the present invention relates to a polymericplasticizer composition having an acid value less than 5 mg KOH/g.

In another aspect the present invention relates to a polymericplasticizer composition having an acid value less than 2 mg KOH/g.

In another aspect the present invention relates to a polymericplasticizer composition having a hydroxyl number less than 80 mg KOH/g.

In another aspect the present invention relates to a polymericplasticizer composition having a hydroxyl number less than 50 mg KOH/g.

In another aspect the present invention relates to a polymericplasticizer composition having a hydroxyl number less than 30 mg KOH/g.

In another aspect the present invention relates to a polymericplasticizer composition having a hydroxyl number less than 25 mg KOH/g.

In another aspect the present invention relates to a polymericplasticizer composition having a polymer backbone ether value less thanabout 5 percent by weight ether oxygen based on the weight of thepolymeric plasticizer composition.

In another aspect the present invention relates to a polymericplasticizer composition wherein the aromatic acid source is an aromaticlinear thermoplastic polyester.

In another aspect the present invention relates to a polymericplasticizer composition wherein the aromatic linear thermoplasticpolyester is selected from polyethylene terephthalate (PET),polybutylene terephthalate, polytrimethylene terephthalate (PTT),polyethylene furanoate, glycol-modified polyethylene terephthalate,copolymers of terephthalic acid and 1,4-cyclohexanedimethanol,isophthalic acid-modified copolymers of terephthalic acid and1,4-cyclohexanedimethanol, copolymers of 2,5-furandicarboxylic acid anda glycol, copolymers of dialkyl 2,5-furandicarboxylate and a glycol,dihydroferulic acid polymers, copolymers of2,2,4,4-tetramethyl-1,3-cyclobutanediol with isophthalic acid,terephthalic acid or orthophthalic derivatives, and combinationsthereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein the aromatic linear thermoplasticpolyester is selected from virgin polyethylene terephthalate, recycledpolyethylene terephthalate, and combinations thereof.

In another aspect the present invention relates to a polymericplasticizer further comprising a thermoplastic polycarbonate, athermoplastic polycarbonate blend with a thermoplastic polyester, athermoplastic polycarbonate transreaction product with a thermoplasticpolyester, and combinations thereof.

In another aspect the present invention relates to a polymericplasticizer composition further comprising poly(bisphenol-A carbonate),a blend or transreaction product of poly(bisphenol-A carbonate) andpolyethylene terephthalate, a blend or transreaction product ofpoly(bisphenol-A carbonate) and polybutylene terephthalate, andcombinations thereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein the glycol is selected from ethyleneglycol, propylene glycol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol,1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol,1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol,2-methyl-1,3-propanediol, neopentyl glycol, glycerol,trimethylolpropane, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol,1,3-cyclohexanedimethanol, diethylene glycol, tetraethylene glycol,dipropylene glycol, triethylene glycol, tripropylene glycol,polyethylene glycol, polypropylene glycol, polycarbonate polyols,pentaerythritol, sorbitol, and block or random copolymer glycols ofethylene oxide and propylene oxide, aliphatic polyester polyols,2,2,4,4-tetramethyl-1,3-cyclobutanediol, and combinations thereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein the glycol is selected from ethyleneglycol, propylene glycol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 1,4-butanediol, 1,4-hexanediol,2-methyl-1,3-propanediol, neopentyl glycol, glycerol,trimethylolpropane, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol,diethylene glycol, tetraethylene glycol, dipropylene glycol, triethyleneglycol, tripropylene glycol, pentaerythritol, sorbitol, and combinationsthereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein the glycol is selected from1,3-butanediol, 1,4-butanediol, propylene glycol, glycerol, neopentylglycol, and combinations thereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein the C₄-C₃₆ monocarboxylic acid isselected from benzoic acid, phenylacetic acid, branched or linearsaturated or unsaturated alkyl carboxylic acids, naphthenic acid,norbornene carboxylic acid, 2-furoic acid, decanoic acid, undecanoicacid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, neodecanoicacid, 2-butyloctanoic acid, 2-ethylhexanoic acid, and combinationsthereof, including esters and anhydrides of these C₄-C₃₆ monocarboxylicacids.

In another aspect the present invention relates to a polymericplasticizer composition wherein the C₄-C₃₆ monocarboxylic acid issubstituted with one or more carbonyl groups.

In another aspect the present invention relates to a polymericplasticizer composition wherein the carbonyl substituted C₄-C₃₆monocarboxylic acid is levulinic acid, or an ester or anhydride thereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein the C₄-C₃₆ monocarboxylic acid ester isa C₁-C₇ alcohol ester of a C₄-C₃₆ monocarboxylic acid.

In another aspect the present invention relates to a polymericplasticizer composition wherein the C₄-C₃₆ monocarboxylic acid ester isselected from alkyl benzoates, alkyl phenylacetates, alkyl esters ofbranched or linear saturated or unsaturated alkyl carboxylic acids,alkyl naphthenoates, alkyl norbornene carboxylates, alkyl 2-furoates,and combinations thereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein the C₄-C₃₆ monocarboxylic anhydride isselected from anhydrides of benzoic acid, phenylacetic acid, branched orlinear saturated or unsaturated alkyl carboxylic acids, naphthenic acid,norbornene carboxylic acid, 2-furoic acid, and combinations thereof.

In another aspect the present invention relates to a polymericplasticizer composition further comprising a C₄-C₃₆ alcohol.

In another aspect the present invention relates to a polymericplasticizer composition wherein the C₄-C₃₆ alcohol is selected fromnorborneol, alkoxylates of branched or linear alkyl phenols, branched orlinear saturated or unsaturated alkyl alcohols, alkoxylated branched orlinear saturated or unsaturated alkyl alcohols, 2-phenoxy ethanol,2-phenoxy propanol, benzyl alcohol, furfuryl alcohol, alkoxylatedfurfuryl alcohol, 2-(hydroxymethyl)tetrahydrofuran,6,6-dimethyl-2-norpinen-2-ethanol, and alkoxylated6,6-dimethyl-2-norpinen-2-ethanol, cyclohexanol, alkoxylatedcyclohexanol, 2-cyclohexylethanol, alkoxylated 2-cyclohexyl ethanol,2-cyclohexyloxyethanol, 1-ethynyl-1-cyclohexanol, 2-phenylethanol,alkoxylated 2-phenyl ethanol, alkoxylated phenols, alkoxylatednorborneol, farnesol, hydrogenated farnesol, geraniol, hydrogenatedgeraniol, and combinations thereof.

In another aspect the present invention relates to a polymericplasticizer composition further comprising a C₃-C₃₆ saturated orunsaturated aliphatic linear, branched, or cyclic polyacid or hydroxylsubstituted polyacid, or esters or anhydrides thereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein the C₃-C₃₆ saturated or unsaturatedaliphatic linear, branched, or cyclic polyacid or hydroxyl substitutedpolyacid, or esters or anhydrides thereof, and combinations thereof,wherein the foregoing polyacid described in this sentence is a diacid.

In another aspect the present invention relates to a polymericplasticizer composition wherein the diacid is selected from succinicacid, glutaric acid, pimelic acid, suberic acid, succinic acid, azelaicacid, sebacic acid, adipic acid, fumaric acid, maleic acid,1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid,1,4-cyclohexane dicarboxylic acid, 2,5-furan dicarboxylic acid,1,9-nonanedioic acid, 1,9-nonenedioic acid, 1,10-decanedioic acid, 1,10,decenedioic acid, 1,11-undecanedioic acid, 1,11-undecenedioic acid,1,18-octadecanedioic acid, 1,18-octadecenedioic acid, 1,12-dodecanedioicacid, 1,12-dodecenedioic acid, 1,14-tetradecanedioic acid,1,14-tetradecenedioic acid, 1,16-hexadecanedioic acid,1,16-hexadecenedioic acid, eicosenedioic acid, eicosanedioic acid,docosanedioic acid; tetracosanedioic acid, tetracosenedioic acid, andcombinations thereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein the C₃-C₃₆ saturated or unsaturatedaliphatic linear, branched, or cyclic polyacid or hydroxyl substitutedpolyacid, or esters or anhydrides thereof, and combinations thereof, isa dimer fatty acid.

In another aspect the present invention relates to a polymericplasticizer composition further comprising a hydroxyl substituted C₃-C₃₆monocarboxylic acid, or ester or anhydride thereof, and combinationsthereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein the hydroxyl substituted C₃-C₃₆monocarboxylic acid, or ester or anhydride thereof is selected from12-hydroxy stearic acid, ricinoleic acid, an alkyl levulinate triolketal, lactic acid, and combinations thereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein the hydroxyl substituted C₃-C₃₆monocarboxylic acid, or ester or anhydride thereof is an alkyllevulinate glycerol ketal.

In another aspect the present invention relates to a polymericplasticizer composition wherein the hydroxyl substituted C₃-C₃₆monocarboxylic acid, or ester or anhydride thereof is ethyl levulinateglycerol ketal.

In another aspect the present invention relates to a polymericplasticizer composition further comprising an aromatic triacid oraromatic tetraacid, or esters or anhydrides thereof, and combinationsthereof; wherein at least one or more of the following (a), (b), or (c)apply to the polymeric plasticizer composition: (a) the polymericplasticizer composition has an acid value of less than 5 mg KOH/g, (b)the C₄-C₃₆ alcohol is not a C₈-C₁₂ alcohol, or (c) the C₄-C₃₆monocarboxylic acid, or ester or anhydride thereof is not a C₁₂-C₁₈monocarboxylic acid.

In another aspect the present invention relates to a polymericplasticizer composition further comprising a hydrophobe.

In another aspect the present invention relates to a polymericplasticizer composition wherein the hydrophobe is selected fromricinoleic acid, castor oil, ethoxylated castor oil, vegetable oils,fatty acids, fatty acid esters, modified vegetable oils, fattytriglycerides, cardanol-derived products, recycled cooking oil,hydroxy-functional materials derived from epoxidized, ozonized, orhydroformylated fatty esters or fatty acids, alkoxylated alkyl phenols,alkoxylated fatty alcohols, and combinations thereof.

In another aspect the present invention relates to a polymericplasticizer composition wherein one or more of the following apply: (a)the weight ratio of aromatic acid source in the polymeric plasticizercomposition is from 5 to 90 weight percent, (b) the weight ratio ofglycol in the polymeric plasticizer composition is from 5 to 70 weightpercent, or (c) the weight ratio of the C₄-C₃₆ monocarboxylic acid, orester or anhydride thereof is from 5 to 80 weight percent.

In another aspect the present invention relates to a polymericplasticizer composition having a recycle content as defined hereingreater than 10 weight percent.

In another aspect the present invention relates to a polymericplasticizer composition having a recycle content as defined hereingreater than 30 weight percent.

In another aspect the present invention relates to a polymericplasticizer composition having a recycle content as defined hereingreater than 50 weight percent.

In another aspect the present invention relates to a polymericplasticizer composition having a recycle content as defined hereingreater than 75 weight percent.

In another aspect the present invention relates to a plasticizedthermoplastic polymer composition comprising (a) from 10% to 80% byweight percent of a polymeric plasticizer composition, and (b) from 20%to 90% by weight of a thermoplastic polymer (that is, a thermoplasticpolymeric material).

In another aspect the present invention relates to a plasticizedcomposition wherein the thermoplastic polymer is selected from polyvinylchloride, polyethylene terephthalate, nitrile butyl rubber,acrylonitrile-butadiene rubber, polyvinyl chloride polyvinyl alcoholcopolymers, acrylates, natural & synthetic rubber, cellulose acetatebutyrate, cellulose nitrate, ethyl cellulose, polyvinyl butyral,chlorinated rubber, polyisoprene, styrene butadiene copolymers,butadiene, halobutyl rubber and combinations thereof.

In another aspect the present invention relates to a plasticizedcomposition wherein the thermoplastic polymer is polyvinyl chloride.

In another aspect the present invention relates to a plasticizercomposition or a plasticized composition further comprising anadditional plasticizer.

In another aspect the present invention relates to a plasticizercomposition or a plasticized composition wherein the additionalplasticizer is selected from di(2-ethylhexyl)phthalate, diisononylphthalate, di-n-butylphthalate, butyl benzyl phthalate, diisodecylphthalate, dioctyl phthalate, diethyl phthalate, diisobutyl phthalate,di-n-hexyl phthalate, trimethyl trimellitate,tri-(2-ethylhexyl)trimellitate, tri-(n-octyl,n-decyl)trimellitate,tri-(heptyl,nonyl)trimellitate, n-octyl trimellitate,bis(2-ethylhexyl)adipate, dimethyl adipate, monomethyl adipate, dioctyladipate, dibutyl sebacate, dibutyl maleate, diisobutyl maleate,benzoates, dioctyl terephthalate/DEHT, 1,2-cyclohexane dicarboxylicacid, diisononyl ester, epoxidized vegetable oils, alkyl sulphonic acidphenyl ester, sulfonamides, N-ethyl toluene sulfonamide, ortho and paraisomers, N-(2-hydroxypropyl)benzene sulfonamide, N-(n-butyl)benzenesulfonamide, organophosphates, tricresyl phosphate, tributyl phosphate,glycols/polyethers, triethylene glycol dihexanoate, tetraethylene glycoldiheptanoate, polybutene, acetylated monoglycerides, alkyl citrates,triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyltributyl citrate, trioctyl citrate, acetyl trioctyl citrate, trihexylcitrate, acetyl trihexyl citrate, butyryl trihexyl citrate, trimethylcitrate, and combinations thereof.

In another aspect the present invention relates to a process forpreparing a polymeric plasticizer composition comprising reacting: (a)an aromatic acid source selected from an aromatic diacid, an aromaticdiacid anhydride, an aromatic diacid monoester, an aromatic diaciddiester, an aromatic linear ester oligomer, an aromatic linearthermoplastic polyester, and combinations thereof; (b) a glycol; and (c)a C₄-C₃₆ monocarboxylic acid, or ester or anhydride thereof at atemperature between 80° C. and 260° C.

In another aspect the present invention relates to a process forpreparing a polymeric plasticizer further comprising performing thereaction in the presence a catalyst.

In another aspect the present invention relates to a process forpreparing a polymeric plasticizer composition wherein the catalyst isselected from titanium catalysts, tin catalysts, and combinationsthereof.

In another aspect the present invention relates to a process forpreparing a polymeric plasticizer composition wherein the catalyst isselected from butyltin tris-2-ethylhexanoate, butylstannoic acid,dibutyltin oxide, tetra-n-butyl titanate, triethanolamine titanium,titanium tetra-isopropoxide, and combinations thereof.

In another aspect the present invention relates to a process forpreparing a polymeric plasticizer further comprising reacting a C₄-C₃₆alcohol.

In another aspect the present invention relates to a process forpreparing a polymeric plasticizer further comprising reacting a C₃-C₃₆saturated or unsaturated aliphatic linear, branched, or cyclic polyacidor hydroxyl substituted polyacid, or esters or anhydrides thereof.

In another aspect the present invention relates to a process forpreparing a polymeric plasticizer further comprising reacting a hydroxylsubstituted C₃-C₃₆ monocarboxylic acid, or ester or anhydride thereof,and combinations thereof.

In another aspect the present invention relates to a process forpreparing a polymeric plasticizer further comprising reacting anaromatic triacid or aromatic tetraacid, or esters or anhydrides thereof,and combinations thereof; where at least one or more of the following(a), (b), or (c) apply: (a) the polymeric plasticizer composition has anacid value of less than 5 mg KOH/g, (b) the C₄-C₃₆ alcohol is not aC₈-C₁₂ alcohol, or (c) the C₄-C₃₆ monocarboxylic acid, or ester oranhydride thereof is not a C₁₂-C₁₈ monocarboxylic acid.

In another aspect the present invention relates to process for preparinga polymeric plasticizer further comprising reacting a hydrophobe.

In another aspect the present invention relates to method ofplasticizing a thermoplastic polymeric material comprising, combining:(a) from 10% to 80% by weight percent of a polymeric plasticizercomposition according to any of claims 1 to 49; and (b) from 20% to 90%by weight of a thermoplastic polymer.

In another aspect the present invention relates to a method ofplasticizing a thermoplastic polymeric material wherein thethermoplastic polymer is selected from polyvinyl chloride, polyethyleneterephthalate, nitrile butyl rubber, acrylonitrile-butadiene rubber,polyvinyl chloride polyvinyl alcohol copolymers, acrylates, natural &synthetic rubber, cellulose acetate butyrate, cellulose nitrate, ethylcellulose, polyvinyl butyral, chlorinated rubber, polyisoprene, styrenebutadiene copolymers, butadiene, halobutyl rubber and combinationsthereof.

In another aspect the present invention relates to a method ofplasticizing a thermoplastic polymeric material, wherein thethermoplastic polymeric material is polyvinyl chloride.

Definitions

As used herein, the following terms have the indicated meanings unlessexpressly stated to the contrary:

The term “aliphatic” as used herein refers to a chemical compoundbelonging to the organic class in which the atoms are not linkedtogether to form an aromatic ring. One of the major structural groups oforganic molecules, the aliphatic compounds include the alkanes, alkenes,and alkynes, including linear, branched, and cyclic variants, andsubstances derived from them—actually or in principle—by replacing oneor more hydrogen atoms by atoms of other elements or groups of atoms.See, Encyclopedia Brittanica, entry which is incorporated by referenceherein in its entirety.

The term “aromatic” as used herein refers to a compound, any of a largeclass of unsaturated chemical compounds characterized by one or moreplanar rings of atoms joined by covalent bonds, which in some depictionsare shown as alternating single and double bonds. The characteristicproperties of these compounds is referred to as aromaticity. Althoughthe term aromatic originally concerned odor, today its use in chemistryis restricted to compounds that have particular electronic, structural,or chemical properties. Aromaticity results from particular bondingarrangements that cause certain π (pi) electrons within a molecule to bestrongly held. Aromaticity is often reflected in smaller than expectedheats of combustion and hydrogenation and is associated with lowreactivity. Benzene (C₆H₆) is the best-known aromatic compound and theparent to which numerous other aromatic compounds are related. See,Encyclopedia Brittanica, which is incorporated by reference herein.

The terms referring to carbon numbers, such as for example C₄-C₃₆ meansthat the chemical group or compounds it is referring to contains theindicated number of carbons or range of carbons, in this example beingfrom four carbon atoms to 36 carbon atoms. This carbon numberingconvention is standard and well known in the art.

The term “polymer backbone ether value” as used herein refers to theoxygen ether content of the polymeric plasticizer composition. In otherwords, the polymer backbone ether value is the ratio of the total oxygenether mass to the mass of the entire polymeric plasticizer, expressed asa weight percentage. The polymer backbone ether value is calculated asfollows as illustrated for a simple chemical compound such astriethylene glycol. Triethylene glycol, which contains two etheroxygens, has a molecular weight (molar mass) of 150.17 grams/mole.

The two ether oxygens of triethylene glycol account for a total mass of31.9988 amu (2×15.9994=31.9988). This total ether oxygen mass is dividedby the molar mass for triethylene glycol and the result is multiplied by100% to give a weight percentage. For triethylene glycol the polymerbackbone ether value is therefore 21.31 weight percent (31.9988 dividedby 150.17×100%=21.31%).

The term “polymeric plasticizer composition” as used herein means thatthe plasticizer composition comprises a polymeric material. Thepolymeric plasticizer is in contrast to monomeric (not containingrepeating monomeric units) or other lower molecular weight plasticizers.An example of such a monomeric or lower molecular weight plasticizer isdiisooctyl phthalate (DOP), which has a molecular weight of 390.56grams/mole.

The polymeric plasticizer compositions useful herein generally have anumber average molecular weight from 500 to 25,000 grams/mole. In otherembodiments these plasticizers have a number average molecular weightfrom 800 to 10,000 grams/mole, and in yet other embodiments theseplasticizers have a number average molecular weight from 1000 to 8000grams/mole.

“Recycle content” as used herein, is determined on a weight percentagebasis by combining the masses of any of the recycled sources used in thepreparation of the polymeric plasticizer composition and dividing by thetotal mass of the polymeric plasticizer composition and multiplying theresult by 100 percent.

The term “recycled polymer” as used herein refers to a polymer that haslittle value after its original lifespan has ended, and is recovered inan economically viable fashion from the original spent application foruse in other applications. An example of a recycle polymer ispolyethylene terephthalate (PET).

The term “waste stream” as used herein refers to waste or discardedproducts from industry, agriculture, or consumer sources that have fewultimate destinations or applications other than for example, landfill,incineration, animal feed, concrete, burning as a source of energy,fertilization, landscaping mulch, or other relatively low valueapplications.

Polymeric Plasticizer Compositions

As stated above, the polymeric plasticizer compositions are polymermaterials, in contrast to monomeric or other lower molecular weightplasticizers. These polymeric plasticizers are made from, or in otherwords are the reaction product of, an aromatic acid source, a glycol,and certain monocarboxylic acid compounds, or esters or anhydridesthereof. These polymeric plasticizers can in some embodiments furthercomprise additional components. Another way of describing thesepolymeric plasticizers is that they comprise repeating units ofmaterials, where the materials are derived from an aromatic acid source,a glycol, and certain monocarboxylic acid compounds, or esters oranhydrides thereof, and any further additional components.

Aromatic Acid Source

The polymeric plasticizer compositions and processes of the presentinvention comprise an aromatic acid source. The aromatic acid source canbe selected from an aromatic diacid, an aromatic diacid anhydride, anaromatic diacid monoester, an aromatic diacid diester, an aromaticlinear ester oligomer, an aromatic linear thermoplastic polyester, andcombinations thereof. The aromatic acid source can be obtained fromrecycled polymers and waste streams. In fact, in view of green chemistryand sustainability considerations, it is highly desirable to usearomatic acid sources from such recycled polymers and waste streams.

Examples of aromatic diacids include phthalic acid, such as 1,2 (orortho), 1,3 (or meta), and 1,4 (or para) phthalic acids, the variousdicarboxylic acids of naphthalene, a non-limiting example of which is1,2-naphthalene dicarboxylic acid, and the dicarboxylic acids of furan,an example of which is 2,5-furan dicarboxylic acid. Anhydrides, as wellas the mono (or half) esters and diesters of these dicarboxylic acidsare contemplated. Another aromatic acid source is aromatic linear esteroligomers such as oligomers which can be derived from thermoplasticpolyesters. Oligomers generally are made up of just a few monomer units.Also, thermoplastic aromatic polyesters, namely the polymeric materialsthemselves, are useful aromatic acid sources, provided thesethermoplastic polyesters are linear, i.e., not containing aromatic tri-or tetra-acids. Thermoplastic polyesters are condensation polymersproduced from the reaction of glycols and aromatic dicarboxylic acids oracid derivatives.

Examples of such thermoplastic polyesters include polyethyleneterephthalate (PET), polybutylene terephthalate, polytrimethyleneterephthalate, polyethylene furanoate, glycol-modified polyethyleneterephthalate, copolymers of terephthalic acid and1,4-cyclohexanedimethanol, isophthalic acid-modified copolymers ofterephthalic acid and 1,4-cyclohexanedimethanol, copolymers of2,5-furandicarboxylic acid and a glycol, copolymers of dialkyl2,5-furandicarboxylate and a glycol, dihydroferulic acid polymers,copolymers of 2,2,4,4-tetramethyl-1,3-cyclobutanediol with isophthalicacid, terephthalic acid or orthophthalic derivatives, and combinationsthereof. See PCT International. Appl. No. WO 2014/075057; ModernPolyesters: Chemistry and Technology of Polyesters and Copolyesters, J.Scheirs and T. Long, eds., Wiley Series in Polymer Science, 2003, JohnWiley & Sons, Ltd. Hoboken, N.J.; Chapters 18-20 of Handbook ofThermoplastics, O. Olabisi, ed., 1997, Marcel Dekker, Inc. New York; andU.S. Pat. Appl. Publ. No. 2009/0131625, the disclosures of which areincorporated herein by reference.

Suitable thermoplastic polyesters include virgin polyesters, recycledpolyesters, or mixtures thereof. Polyethylene terephthalate (PET) isparticularly preferred, especially recycled polyethylene terephthalate(rPET), virgin PET, and mixtures thereof. For more examples of suitablethermoplastic polyesters, see U.S. Pat. Appl. Publ. No. 2009/0131625,the teachings of which are incorporated herein by reference.

Recycled polyethylene terephthalate suitable for use in making theinventive polymeric plasticizer compositions can come from a variety ofsources. The most common source is the post-consumer waste stream of PETfrom plastic bottles or other containers. Another possible source isfrom the post-industrial waste stream of PET from the production offibers, bottles, or other containers or articles. The recycled PET(rPET) can be colorless or contain dyes (e.g., green, blue, brown, orother colors) or be mixtures of these. A minor proportion of organic orinorganic foreign matter (e.g., paper, other plastics, glass, metal,etc.) can be present. A desirable source of rPET is “flake” rPET, fromwhich many of the common impurities present in scrap PET bottles havebeen removed in advance. Another desirable source of rPET is pelletizedrPET, which is made by melting and extruding rPET through metalfiltration mesh to further remove particulate impurities. Because PETplastic bottles are currently manufactured in much greater quantity thanany recycling efforts can match, scrap PET will continue to be availablein abundance.

Glycols

The polymeric plasticizer compositions and processes of the presentinvention comprise a glycol. Glycols suitable for use herein are wellknown. By “glycol,” is meant a linear or branched, aliphatic or cyclic,aliphatic compound or mixture of compounds having two or more hydroxylgroups. Other functionalities, particularly ether or ester groups, maybe present in the glycol. In preferred glycols, two of the hydroxylgroups are separated by from 2 to about 20 carbon atoms, preferably fromabout 2 to about 14 carbon atoms, and more preferably from about 2 toabout 8 carbon atoms. Note that ether linkages may be included in thecarbon separation between hydroxyl groups, though the oxygen atoms arenot included in the carbon count. Suitable glycols include, for example,ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol,1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol,1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol,2-methyl-1,3-propanediol, neopentyl glycol, glycerol (also known asglycerin or glycerine), trimethylolpropane, 3-methyl-1,5-pentanediol,1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, diethylene glycol,tetraethylene glycol, dipropylene glycol, triethylene glycol,tripropylene glycol, polyethylene glycol, polypropylene glycol,polycarbonate polyols, pentaerythritol, sorbitol, and block or randomcopolymer glycols of ethylene oxide and propylene oxide, aliphaticpolyester polyols, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, andcombinations thereof.

C₄-C₃₆ Monocarboxylic Acids, Esters, and Anhydrides

The polymeric plasticizer compositions and processes of the presentinvention comprise a C₄-C₃₆ monocarboxylic acid, or ester or anhydridethereof. By “monocarboxylic acid”, it is meant that the acid, or theester or anhydride derived therefrom is based on a carboxylic acidcompound having a single carboxylic acid group. An example of such acarboxylic acid is the C₆ monocarboxylic acid, hexanoic acid. An exampleof an ester is the ethyl ester of hexanoic acid, which is known as ethylhexanoate. An example of an anhydride is hexanoic acid anhydride, whichis also known as hexanoic anhydride. Also, the anhydride can be a mixedanhydride from two different carboxylic acids, as long as one of theacids is from a C₄-C₃₆ monocarboxylic acid. Such an example would be themixed anhydride of hexanoic acid (a C₆ monocarboxylic acid, which meetsthe C₄-C₃₆ requirement) and acetic acid (a C₂ acid).

In general, the C₄-C₃₆ monocarboxylic acid, or ester or anhydridethereof can function as a chain terminator in the preparation of thepolymeric plasticizer compositions, because when it is incorporated intothe polymerization reaction, it can cap the ends of the polymer chainstructure.

The C₄-C₃₆ monocarboxylic acid, or ester or anhydride thereof can beselected from straight, branched or cyclic aliphatic compounds that canbe either saturated or unsaturated. Furthermore, aromatic compounds arealso intended. Additionally, for the esters, the alcohol-derived portionis preferably derived from an alcohol having from one to seven carbonatoms, i.e. C₁ to C₇. Also, for the foregoing compounds described inthis paragraph, the carbon backbones can be further substituted with oneor more carbonyl —(C═O)-groups.

Examples of C₄-C₃₆ monocarboxylic acids include benzoic acid,phenylacetic acid, branched or linear saturated or unsaturated alkylcarboxylic acids, naphthenic acid, norbornene carboxylic acid, 2-furoicacid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid,tetradecanoic acid, neodecanoic acid, 2-butyloctanoic acid,2-ethylhexanoic acid, and combinations thereof. C₄-C₃₆ monocarboxylicacids in which the carbon backbone is further substituted with one ormore carbonyl groups (═O) are useful herein, an example being levulinicacid.

Examples of C₄-C₃₆ monocarboxylic acid esters include C₁ to C₇ alcoholesters of the C₄-C₃₆ monocarboxylic acids, in other words C₄-C₃₆monocarboxylic acids that have been esterified with C₁ to C₇ alcohols.These C₁ to C₇ alcohols can include aromatic alcohols. Examples ofC₄-C₃₆ monocarboxylic acid esters include alkyl benzoates, alkylphenylacetates, alkyl esters of branched or linear saturated orunsaturated alkyl carboxylic acids, alkyl naphthenoates, alkylnorbornene carboxylates, alkyl 2-furoates, and combinations thereof.

Examples of C₄-C₃₆ monocarboxylic anhydrides include anhydrides ofbenzoic acid, benzene acetic acid, branched or linear saturated orunsaturated alkyl carboxylic acids, naphthenic acid, norbornenecarboxylic acid, 2-furoic acid, and combinations thereof. Additionally,the anhydrides can include mixed anhydrides derived from two differentcarboxylic acids, such as a mixed anhydride of benzoic acid and benzeneacetic acid.

Other Components of the Polymeric Plasticizer Compositions

The polymeric plasticizer compositions and processes of the presentinvention can, in some embodiments comprise further components. In somecases, these other components can function as a chain builder in thepreparation of the polymeric plasticizer compositions, because whenincorporated into the polymer chain they tend to contribute to furtherthe polymerization reaction, thereby increasing the molecular weight ofthe resultant polymer.

C₄-C₃₆ Mono Alcohols

The polymeric plasticizer compositions and processes of the presentinvention can further comprise a C₄-C₃₆ mono alcohol. It is understoodthat these C₄-C₃₆ alcohols are intended to be distinct from the requiredglycol (i.e. the diol) of the present invention. It is intended thatalcohols lower than C₄ generally are too volatile and do not havedesirable characteristics for incorporation herein. The C₄-C₃₆ alcoholcan be selected from straight, branched or cyclic aliphatic compoundsthat can be either saturated or unsaturated. Aromatic compounds are alsointended. Also, alkoxylated alcohols are contemplated herein.

Useful C₄-C₃₆ alcohols include those selected from norborneol,alkoxylates of branched or linear alkyl phenols, branched or linearsaturated or unsaturated alkyl alcohols, alkoxylated branched or linearsaturated or unsaturated alkyl alcohols, 2-phenoxy ethanol, 2-phenoxypropanol, benzyl alcohol, furfuryl alcohol, alkoxylated furfurylalcohol, 2-(hydroxymethyl)tetrahydrofuran,6,6-dimethyl-2-norpinen-2-ethanol, and alkoxylated6,6-dimethyl-2-norpinen-2-ethanol, cyclohexanol, alkoxylatedcyclohexanol, 2-cyclohexylethanol, alkoxylated 2-cyclohexyl ethanol,2-cyclohexyloxyethanol, 1-ethynyl-1-cyclohexanol, 2-phenylethanol,alkoxylated 2-phenyl ethanol, alkoxylated phenols, alkoxylatednorborneol, farnesol, hydrogenated farnesol, geraniol, hydrogenatedgeraniol, and combinations thereof.

Aliphatic Polyacids

The polymeric plasticizer compositions and processes of the presentinvention can further comprise a C₃-C₃₆ saturated or unsaturatedaliphatic linear, branched, or cyclic polyacid, or esters or anhydridesthereof. By polyacid is meant that the acid compound contains two ormore carboxylate groups. Diacids as well as dimer fatty acids areintended, as well as polyacids having three (triacids), four(tetraacids), or more carboxylate groups. Dimer fatty acids, ordimerized fatty acids is a term used in the art to describe dicarboxylicacids prepared by dimerizing unsaturated fatty acids. Also, for theforegoing compounds described in this paragraph, the carbon backbonescan be further substituted with one or substituents including forexample, —F, —OH, —SH, and carbonyl —(C═O)—. An example of such an aciduseful herein is citric acid.

Examples of diacids include succinic acid, glutaric acid, pimelic acid,suberic acid, succinic acid, pimelic acid azelaic acid, sebacic acid,adipic acid, fumaric acid, maleic acid, 1,2-cyclohexane dicarboxylicacid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylicacid, 2,5-furan dicarboxylic acid, 1,9-nonanedioic acid, 1,9-nonenedioicacid, 1,10-decanedioic acid, 1,10-decenedioic acid, 1,11-undecanedioicacid, 1,11-undecenedioic acid, 1,18-octadecanedioic acid,1,18-octadecenedioic acid, 1,12-dodecanedioic acid, 1,12-dodecenedioicacid, 1,14-tetradecanedioic acid, 1,14-tetradecenedioic acid,1,16-hexadecanedioic acid, 1,16-hexadecenedioic acid, eicosenedioicacid, eicosanedioic acid, docosanedioic acid, tetracosanedioic acid,tetracosendioic acid, and combinations thereof. Esters and anhydrides ofthe fatty diacids are also contemplated herein.

Dimer fatty acids are made by dimerizing unsaturated fatty acids (e.g.,oleic acid, linoleic acid, linolenic acid, ricinoleic acid) in thepresence of a catalyst, such as a bentonite or montmorillonite clay.Commercially available dimer fatty acids are usually mixtures ofproducts in which the dimerized product predominates, however,trimerized products may also result and be included as a significantportion of the dimer fatty acid product, and are included herein in thisdefinition. Some commercial dimer acids are made by dimerizing tall oilfatty acids. Dimer fatty acids frequently have 36 carbons and twocarboxylic acid groups. However, the trimerized co-products may contain54 carbons. They may be saturated or unsaturated. They may also behydrogenated to remove unsaturation. In a preferred aspect, the dimerfatty acid comprises dimerized oleic acid, trimerized oleic acid,dimerized linoleic acid, trimerized linolelic acid, dimerized linolenicacid, trimerized linolenic acid, or mixtures thereof. Suitable dimerfatty acids include Pripol™ dimer fatty acids (products of Croda) suchas Pripol™ 1006, 1009, 1010, 1012, 1013, 1017, 1022, 1025, 1027, 1029,1036, and 1098; Unidyme™ dimer acids (products of Arizona Chemical) suchas Unidyme 10, 14, 18, 22, 35, M15, and M35; dimer acids available fromEmery Oleochemicals, and FloraDyme™ dimer acids from FlorachemCorporation. Methods for synthesizing dimer fatty acids suitable for useare also known. Fatty acids having at least one carbon-carbon doublebond are dimerized in the presence of a catalyst such as amontmorillonite, kaolinite, hectorite, or attapulgite clay (see, e.g.,U.S. Pat. Nos. 2,793,220, 4,371,469, 5,138,027, and 6,281,373, theteachings of which are incorporated herein by reference; see also WO2000/075252 and CA 104511).

Hydroxyl Substituted C₃-C₃₆ Carboxylic Acids

The polymeric plasticizer compositions and processes of the presentinvention can further comprise a hydroxyl substituted C₃-C₃₆ carboxylicacid, or ester or anhydride thereof, and combinations thereof.Generally, these hydroxyl substituted, or hydroxy acids, are aliphaticmonocarboxylic acids and can be straight, branched or cyclic, and can besaturated or unsaturated. Examples of these hydroxyl acids include12-hydroxy stearic acid, ricinoleic acid, citric acid, lactic acid, andcombinations thereof.

Hydroxyl substituted carboxylic acids are further described in U.S. Pat.No. 5,206,341, to Ibay et al., issued Apr. 27, 1993, which isincorporated by reference herein in its entirety. Also,polyhydroxyalkanoates (PHAs) are useful herein. PHAs are naturallyproduced by numerous microorganisms as energy reserve materials in thepresence of an excess carbon source when an essential nutrient, such asnitrogen or phosphorous is available only in limiting concentrations.PHAs also form part of depsipeptides, bio-oligomers ubiquitous in naturewhich are composed of hydroxyl and amino acids linked by amide and esterbonds.

Included within the definition of hydroxyl substituted C₃-C₃₆ carboxylicacids, or esters or anhydrides thereof are compounds such as alkyllevulinate triol ketals. These compounds have a free hydroxyl group andare intended to meet the definition, and are distinct from theoptionally carbonyl-containing C₄-C₃₆ monocarboxylic acids, or ester oranhydride thereof also described herein, an example of which waslevulinic acid (which does not have a hydroxyl group). An example of analkyl levulinate triol ketal is ethyl levulinate glycerol ketal.

In some aspects, the polymeric plasticizer compositions and processescomprise recurring units from a hydroxy-functional ketal acid, ester oranhydride. Suitable hydroxy-functional ketal acids, esters, andanhydrides can be made by reacting oxocarboxylates with a triol,preferably in the presence of an acid catalyst. As used herein, and forconvenience, “ketal” refers to either a hydroxy-functional ketal(reaction product of a triol and a ketone) or a hydroxy-functionalacetal (reaction product of a triol and an aldehyde).

Suitable oxocarboxylates have a ketone or aldehyde (“oxo”) functionalityin addition to a carboxylate (acid, ester, or anhydride) functionality.The carbonyl groups of the ketone or aldehyde may or may not beseparated by one or more carbons from the acid, ester, or amidecarbonyl.

Suitable oxocarboxylates include keto acids, keto esters, ketoanhydrides, aldo acids, aldo esters, and aldo anhydrides.

Suitable keto acids include, for example, pyruvic acid, acetoaceticacid, levulinic acid, oxaloacetic acid, 2-ketobutyric acid,2-ketovaleric acid, homolevulinic acid, 4-acetylbutyric acid,3-ketohexanoic acid, 5-acetylvaleric acid, and the like.

Suitable keto esters are lower (e.g., C₁-C₁₀, preferably C₁-C₆) alkyl oralkenyl esters of the keto acids. Suitable alcohols used for making theesters from the keto acids include, for example, methanol, ethanol,1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-hexanol, and the like,with methyl esters and ethyl esters being most preferred. Thus, suitableketo esters include, for example, ethyl pyruvate, ethyl acetoacetate,methyl acetoacetate, ethyl levulinate, ethyl 4-acetylbutyrate, and thelike.

Suitable aldo acids include, for example, 2-oxoacetic acid,3-oxopropanoic acid, 2-methyl-3-oxopropanoic acid, 4-oxobutanoic acid,2-methyl-4-oxobutanoic acid, 3-methyl-4-oxobutanoic acid, 5-oxopentanoicacid, 2-methyl-5-oxopentanoic acid, 3-methyl-5-oxopentanoic acid,4-methyl-5-oxopentanoic acid, 6-oxohexanoic acid, 5-methyl-6-oxohexanoicacid, and the like.

Suitable aldo esters are lower (e.g., C₁-C₁₀, preferably C₁-C₆) alkyl oralkenyl esters of the aldo acids. Suitable alcohols used for making theesters from the aldo acids include, for example, methanol, ethanol,1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-hexanol, and the like,with methyl esters and ethyl esters being most preferred. Thus, suitablealdo esters include, for example, ethyl 3-oxopropanoate, methyl4-oxobutanoate, ethyl 6-oxohexanoate, and the like.

For additional examples of suitable oxocarboxylates, see U.S. Pat. Nos.8,604,077; 8,546,519; and 8,053,468, the teachings of which areincorporated herein by reference.

The hydroxy-functional ketal acids, esters, and amides can be made byreacting oxocarboxylates with a triol. Suitable triols have arerelatively low molecular weight compounds having three hydroxyl groups.Examples include glycerol, trimethylolpropane, trimethylolethane,1,2,4-butanetriol, 1,2,5-trihydroxypentane, and the like. Glycerol,trimethylolpropane, and trimethylolethane are readily available and arepreferred for some aspects. For additional examples of suitable triols,see U.S. Pat. Nos. 8,604,077; 8,546,519; and 8,053,468, the teachings ofwhich are incorporated herein by reference.

The reaction of an oxycarboxylate and a triol, in some aspects in thepresence of an acid catalyst, provides a hydroxy-functional ketal acid,ester, or amide. Suitable acid catalysts for this reaction are wellknown and include mineral acids, organic acids, solid acids, organicclays, and the like. Organic sulfonic acids, such as p-toluenesulfonicacid, are particularly preferred.

In some aspects, the hydroxy-functional ketal acid, ester, or amide hasthe general structure:

wherein R¹ is hydrogen, methyl, ethyl, or hydroxymethyl; R² is hydrogen,C₁-C₂₄ alkyl, or C₁-C₂₄ alkenyl; Z is a C₁-C₆ alkylene group or a C₁-C₆alkylene group substituted with a C₁-C₂₄ alkyl or alkenyl group; X isOR³; R³ is hydrogen or a C₁-C₁₂ alkyl group or carboxylate; m is 0 or 1;and n is 0 or 1. In some aspects, X is preferably OR³, and R³ is aC₁-C₁₂ alkyl group.

Hydroxy-functional ketal esters are preferred. Suitablehydroxy-functional ketal esters include, for example, ethyl levulinateglycerol ketal, methyl levulinate trimethylolpropane ketal, ethyllevulinate trimethylolpropane ketal, ethyl pyruvate glycerol ketal,ethyl pyruvate triethylolpropane ketal, ethyl acetoacetate glycerolketal, and the like. In some aspects, levulinate glycerol ketals arepreferred hydroxy-functional ketal esters.

Aromatic Triacids and Tetraacids

The polymeric plasticizer compositions and processes of the presentinvention can further comprise triacids and tetraacids. Examples ofthese acids include the benzene tricarboxylic acids, such asbenzene-1,2,3-tricarboxylic acid (which is also known as hemimelliticacid), benzene-1,2,4-tricarboxylic acid (which is also known astrimellitic acid), and benzene-1,2,5-tricarboxylic acid (which is alsoknown as trimesic acid), and also the tetracarboxylic acidbenzene-1,2,4,5-tetracarboxylic acid. Other examples include thenaphthalene tricarboxylic acids and tetracarboxylic acids. Also, usefulherein are esters and anhydrides of the tricarboxylic andtetracarboxylic acids, as well as mixtures of the compounds.

In some alternative embodiments, when the compositions and processescomprise an aromatic triacid or tetraacid, or ester, or anhydridethereof, then at least one or more of the following (a), (b), or (c)apply to the polymeric plasticizer composition: (a) the polymericplasticizer composition has an acid value of less than 5 mg KOH/g, (b)the C₄-C₃₆ alcohol is not a C₈-C₁₂ alcohol, or (c) the C₄-C₃₆monocarboxylic acid, or ester or anhydride thereof is not a C₁₂-C₁₈monocarboxylic acid.

Hydrophobes

The polymeric plasticizer compositions and processes of the presentinvention can further comprise a hydrophobe. Hydrophobes includetriglycerides and modified triglycerides, fatty acids, fatty acidesters, fatty diacids, vegetable oils and modified vegetable oils (forexample as described in U.S. Pat. No. 5,922,779, U.S. Pat. No.6,359,022, U.S. Pat. No. 6,664,363, and WO 2013/154874A1); castor oil(for example, as described in WO 2013/154874A1); modified or derivatizedpolyterpenes; modified cashew nut shell oil; cardanol; derivatives ofcardanol; Diels Alder or ene reaction modified polyols (for example, asdescribed in WO 2013/109834); and tall oil fatty acids (for example, asdescribed in U.S. Pat. No. 5,075,417 and U.S. Pat. No. 4,897,429).

Examples of triglycerides suitable for the practice of this inventioninclude soybean oil, algae oil, yeast oil, bacterial oil, animal tallow,fish oil, canola oil, castor oil, tung oil, linseed oil, corn oil,recycled cooking oil, sunflower oil, palm oil, peanut oil, palm kerneloil, cottonseed oil, coconut oil, and safflower oil.

Examples of fatty acids suitable for the practice of this inventioninclude linoleic, myristic, palmitic, caproic, caprylic, capric, 2-ethylhexanoic, lauric, stearic, oleic, linolenic, ricinoleic, tall oil, andmixtures thereof. The alkyl esters of these fatty acids and mixtures ofthese alkyl esters thereof are also suitable examples for the practiceof this invention.

Examples of hydrophobes include those selected from ricinoleic acid,castor oil, ethoxylated castor oil, vegetable oils, fatty acids, fattyacid esters, modified vegetable oils, fatty triglycerides,cardanol-derived products, recycled cooking oil, hydroxy-functionalmaterials derived from epoxidized, ozonized, or hydroformylated fattyesters or fatty acids, alkoxylated alkyl phenols, alkoxylated fattyalcohols, and combinations thereof.

Thermoplastic Polycarbonates

The polymeric plasticizer compositions and processes of the presentinvention can further comprise a thermoplastic polycarbonate (PC).Polycarbonates are polymers containing repeating units connected bycarbonate functional groups. Many polycarbonates of commercial interestare derived from rigid monomers. A balance of useful features includingtemperature resistance, impact resistance and optical propertiesposition polycarbonates between commodity plastics and engineeringplastics. Polycarbonates can be produced by the reaction of bisphenol A(BPA) and phosgene. Examples of polycarbonates useful here includeLexan®, Calibre®, and Makrolon®. Polycarbonate is coded 7 implying thatit is difficult to recycle, however, polycarbonate bottles and CDs arebeing extensively recycled. One method of recycling polycarbonate is bychemical recycling. Polycarbonate is made to react with phenol in thepresence of a catalyst to form BPA and diphenyl carbonate (DPC)monomers. After purification, both these monomers are used to producethe polymer. Also useful herein is a thermoplastic polycarbonate blendwith a thermoplastic polyester, a thermoplastic polycarbonatetransreaction product with a thermoplastic polyester, and combinationsthereof. Yet, other useful materials include poly(bisphenol-Acarbonate), a blend or transreaction product of poly(bisphenol-Acarbonate) and polyethylene terephthalate, a blend or transreactionproduct of poly(bisphenol-A carbonate) and polybutylene terephthalate,and combinations thereof.

Other Plasticizers

The polymeric plasticizer compositions and processes of the presentinvention can further comprise other plasticizers. Generally, theseother plasticizers are monomeric or low molecular weight plasticizersthat are well known. However, higher molecular weight and otherpolymeric plasticizers can be used. Examples of these other plasticizersinclude plasticizers selected from diooctyl phthalate (DOP) [which isalso known as di(2-ethylhexyl)phthalate (DEHP) or bis-ethylhexylphthalate, or diisooctyl phthalate (DIOP)], diisononyl phthalate (DINP),di-n-butylphthalate (DnBP, DBP), butyl benzyl phthalate (BBzP),diisodecyl phthalate (DIDP), dioctyl (straight chain octyl) phthalate,diethyl phthalate (DEP), diisobutyl phthalate (DIBP), di-n-hexylphthalate, trimethyl trimellitate (TMTM), tri-(2-ethylhexyl)trimellitate(TEHTM-MG), tri-(n-octyl,n-decyl)trimellitate (ATM),tri-(heptyl,nonyl)trimellitate (LTM), n-octyl trimellitate (OTM),bis(2-ethylhexyl)adipate (DEHA), dimethyl adipate (DMAD), monomethyladipate (MMAD), dioctyl adipate (DOA), dibutyl sebacate (DBS), dibutylmaleate (DBM), diisobutyl maleate (DIEM), benzoates, dioctylterephthalate/DEHT, 1,2-cyclohexane dicarboxylic acid, diisononyl ester(BASF trademark: DINCH), epoxidized vegetable oils, alkyl sulphonic acidphenyl ester (ASE), sulfonamides, N-ethyl toluene sulfonamide (o/pETSA), ortho and para isomers, N-(2-hydroxypropyl)benzene sulfonamide(HP BSA), N-(n-butyl)benzene sulfonamide (BBSA-NBBS), organophosphates,tricresyl phosphate (TCP), tributyl phosphate (TBP), glycols/polyethers,triethylene glycol dihexanoate (3G6, 3GH), tetraethylene glycoldiheptanoate (4G7), polybutene, acetylated monoglycerides, alkylcitrates, triethyl citrate (TEC), acetyl triethyl citrate (ATEC),tributyl citrate (TBC), acetyl tributyl citrate (ATBC), trioctyl citrate(TOC), acetyl trioctyl citrate (ATOC), trihexyl citrate (THC), acetyltrihexyl citrate (ATHC), butyryl trihexyl citrate (BTHC, trihexylo-butyryl citrate), trimethyl citrate (TMC), and combinations thereof.

Properties of the Polymeric Plasticizer Compositions

The polymeric plasticizer compositions can have a wide range of physicaland chemical properties. The following are examples of such usefulproperties.

The polymeric plasticizer compositions will generally have a numberaverage molecular weight from 500 to 25,000 grams/mole. It is generallyfound that polymeric, as opposed to lower weight monomeric, plasticizercompositions are desirable for compatibility with the polymers to beplasticized and to provide the desirable plasticizing effects. Othermolecular weight ranges for the polymeric plasticizer compositionsinclude a number average molecular weight from 800 to 10,000 grams/mole,and a number average molecular weight from 1000 to 8000 grams/mole.

The polymeric plasticizer compositions will generally have a low acidvalue and a low hydroxyl value, as such low values are generallypreferred for compatibility with the polymers to be plasticized, andalso to avoid unwanted breakdown and failure of the polymer. Thepolymeric plasticizer compositions generally have an acid value lessthan 10 mg KOH/g. In further embodiments, the polymeric plasticizercompositions have an acid value less than 5 mg KOH/g. In yet furtherembodiments, the polymer plasticizer compositions have an acid valueless than 2 mg KOH/g.

The polymeric plasticizer compositions generally have a hydroxyl numberless than 80 mg KOH/g. In further embodiments, the polymeric plasticizercompositions have a hydroxyl number less than 50 mg KOH/g. In yetfurther embodiments, the polymeric plasticizer compositions have ahydroxyl number less than 30 mg KOH/g. In yet further embodiments, thepolymeric plasticizer compositions have a hydroxyl number less than 25mg KOH/g.

Polymer plasticizer compositions having a low polymer backbone ethervalue are desirable and generally have good compatibility with thepolymer to be plasticized and desirable performance characteristics. Thegenerally, the polymeric plasticizer compositions have a polymerbackbone ether value less than about 5 percent by weight ether oxygenbased on the weight of the polymeric plasticizer.

The following weight ratios of the polymeric plasticizer compositioncomponents are useful: A polymeric plasticizer composition wherein theweight ratio of aromatic acid source in the polymeric plasticizercomposition is from 5 to 90 weight percent. A polymeric plasticizercomposition wherein the weight ratio of glycol in the polymericplasticizer composition is from 5 to 70 weight percent. A polymericplasticizer composition wherein the weight ratio of the C₄-C₃₆monocarboxylic acid, or ester or anhydride thereof is from 5 to 80percent.

The polymeric plasticizer compositions can have a wide range ofviscosity. For example, polymeric plasticizers having a viscosity at 25°C. of from about 100 to about 300,000 cP are useful herein. Viscositycan be determined by any industry-accepted method. It is convenient touse, for instance, a Brookfield viscometer (such as a Brookfield DV-IIIUltra rheometer) fitted with an appropriate spindle, and to measure asample at several different torque settings to ensure an adequateconfidence level in the measurements. Viscosity measurements can also bemade at other temperatures.

Recycle Content

Because of environmental and resource concerns it is also desirable tohave polymeric plasticizer compositions made from recycled materials,particularly with respect to the aromatic acid source. An advantage ofsuch polymeric plasticizer compositions made from recycled sources onbio- or petrochemical sources for raw material. The present inventionprovides a means for recycling both the aromatic acid source, and alsothe other components described herein to provide a polymeric plasticizerhaving a high recycle content.

The glycols used herein can also be obtained from recycle sources. Someglycols, such as propylene glycol or ethylene glycol, are available asrecovered or recycled materials. For instance, propylene glycol is usedin deicing fluids, and after use, it can be recovered, purified, andreused. Additionally, recycled ethylene glycol may be obtained fromrecovered engine antifreeze or engine coolant. Preferably, thedigestible polymer is prepared or obtained from renewable resources orpost-consumer or post-industrial recycled sources.

By “recycle content,” we mean the combined amounts of recycled aromaticacid source from, e.g. a thermoplastic polyester and any recycled glycolor C₄-C₃₆ monocarboxylic acid, or ester or anhydride thereof or of thefurther C₄-C₃₆ alcohol. Recycle content can be calculated, for instance,by combining the masses of recycled thermoplastic polyester and anyrecycled glycol, etc., dividing this sum by the total mass of reactants(glycols, thermoplastic polyester, and digestible polymer), and thenmultiplying the result by 100. The recycle content can range from 1 to90 weight percent. In general, it is desirable that the recycle contentas defined herein is greater than 10 weight percent. In otherembodiments, it is desirable that the recycle content as defined hereinis greater than 30 weight percent. In yet further embodiments, it isdesirable that the recycle content as defined herein is greater than 50weight percent. In yet further embodiments, it is desirable that therecycle content as defined herein is greater than 75 weight percent.

Processes for Preparing Polymeric Plasticizer Compositions

The polymeric plasticizer compositions can be used to plasticize avariety of polymeric materials, particularly thermoplastic polymers. Thethermoplastic polymer can be selected from polyvinyl chloride (PVC),polyethylene terephthalate (PET), NBR (nitrile butyl rubber),acrylonitrile-butadiene rubber, PVC-PVA (polyvinyl alcohol) copolymers,acrylates, natural & synthetic rubber, CAB (cellulose acetate butyrate),CN (cellulose nitrate), EC (ethyl cellulose), PVB (polyvinyl butyral),chlorinated rubber, polyisoprene, styrene butadiene copolymers,butadiene, halobutyl rubber and combinations thereof. A particularlyimportant polymer of commercial interest that can be plasticized withthe polymeric plasticizer compositions herein is PVC. PVC is used in awide variety of industrial and consumer applications.

The polymeric plasticizer composition can be made in either a stepwiseprocess or in a single step process, depending on the aromatic acidsource. In the instance when a thermoplastic polyester is used as anaromatic acid source, it is desirable to use a two-step process in whichthe first step is the glycolysis of the thermoplastic polyester followeda second step involving further esterification or transesterificationreactions. In most other cases, a one step process is suitable.

When used as a starting source, the thermoplastic polyester and glycolare heated, optionally in the presence of a catalyst, to give a digestedintermediate. The digested intermediate will commonly be a mixture ofglycol reactant, glycol(s) generated from the thermoplastic polyester,terephthalate oligomers, and other glycolysis products. For example,when PET or rPET is the thermoplastic polyester, the digestedintermediate will include a mixture of glycol reactant, ethylene glycol(generated from the PET or rPET), bis(2-hydroxyalkyl)terephthalate(“BHAT”), higher PET oligomers, and other glycolysis products. Similardigested mixtures in various forms have been made and characterizedpreviously (see, e.g., D. Paszun et al., Ind. Eng. Chem. Res. 36 (1997)1373 and N. Ikladious, J. Elast. Plast. 32 (2000) 140), which areincorporated by reference herein in their entirety. Heating isadvantageously performed at temperatures within the range of 80° C. to260° C. Other temperature ranges include, 130° C. to 250° C., 150° C. to250° C., 160° C. to 250° C., and 160° C. to 220° C.

More specifically, in the context of the present invention, glycolysisrefers to the reaction of the hydroxyl group of a digested aromaticpolyacid source, e.g., a thermoplastic polyester to reduce the molecularweight of the thermoplastic polyester thereby providing a polyol that isa liquid at temperatures between 20° C. and 120° C.

In one aspect, when the thermoplastic polyester is polyethyleneterephthalate, the glycolysis intermediate comprises a glycol or mixtureof glycols and a terephthalate component. The thermoplastic polyestercomponents can be digested by glycols via a transesterification reactionand this digestion reaction is performed by heating the thermoplasticpolyester, glycol(s), and any catalyst at least until the mixtureliquefies and particles of the thermoplastic polyester are no longerapparent at the temperature of the reaction. The glycolysis reactiontimes range from about 30 minutes to about 16 hours, more typically 1 to10 hours, even more typically 3 to 8 hours, and will depend on thereaction temperature, source of the thermoplastic polyester, theparticular glycol reactant used, mixing rate, desired degree ofdepolymerization, and other factors that are within the skilled person'sdiscretion.

The glycolysis products usually further react with carboxylic acids,esters, and anhydrides to complete the plasticizer compositionsynthesis. An appropriate distillation apparatus is utilized toeliminate condensation reaction by-products, such as water, ethanol,etc., and to minimize undesired glycol loss, which could lead to lessreaction control.

Catalysts

Catalysts suitable for making the polymeric plasticizers are well known.See, e.g., K. Troev et al., J. Appl. Polym. Sci. 90 (2003) 1148, whichis incorporated by reference herein in its entirety. In particular,suitable catalysts comprise titanium, zinc, antimony, germanium,zirconium, tin, manganese, or other metals. Specific examples includetitanium alkoxides (e.g., tetrabutyl titanate), titanium(IV) phosphate,zirconium alkoxides, zinc acetate, lead acetate, cobalt acetate,manganese(II) acetate, antimony trioxide, germanium oxide, or the like,and mixtures thereof. In some embodiments, the catalyst is selected fromtitanium catalysts, tin catalysts, and combinations thereof. Examples ofcatalysts include butyltin tris-2-ethylhexanoate, butylstannoic acid,dibutyltin oxide, tetra-n-butyl titanate, triethanolamine titanium,titanium tetra-isopropoxide, and combinations thereof. The amount ofcatalyst used is typically in the range of 0.005 to 5 wt. %, preferably0.01 to 1 wt. %, more preferably 0.05% to 0.1 wt. %, based on the totalamount of polymeric plasticizer composition being prepared. Because ofthe relatively small amount of the catalyst used, it is often moreconvenient to determine the amount of catalyst in parts per million(ppm) based on the total composition of the polymeric plasticizercomposition. The weight percentage ranges of 0.005 to 5 wt. %, 0.01 to 1wt. %, and 0.05% to 0.1 wt. %, correspond to the following ranges in ppmrespectively: 5 to 50,000 ppm, 50 to 10,000 ppm, and 500 to 1000 ppm.

Plasticized Polymer Compositions

Plasticized polymer compositions are prepared by combining the polymericplasticizer composition and the polymer to be plasticized, such as forexample PVC, using methods well known in the art. Other additives can beused such as fillers, lubricants, antidegradants, and heat stabilizers,depending on the application and performance requirements. See, Ed.Richard F. Grossman, “Handbook of Vinyl Formulating, 2^(nd) edition,(Wiley) April 2008, which is incorporated by reference herein in itsentirety.

In general the plasticized compositions comprise from 10% to 90% byweight percent of the polymeric plasticizer composition and from 10% to90% by weight percent of the polymer to be plasticized, such as athermoplastic polymer. Other ranges for the plasticized compositionscomprise from 15% to 85% by weight percent of the polymeric plasticizercomposition and from 15% to 85% by weight percent of the polymer to beplasticized. Yet other ranges for the plasticized compositions comprisefrom 10% to 80% by weight percent of the polymeric plasticizercomposition and from 20% to 90% by weight percent of the polymer to beplasticized.

Testing and Evaluation Methods

Properties of the polymeric plasticizer compositions and plasticizedpolymers prepared therefrom are evaluated using various tests andmethods well known in the art. The evaluation of the compositions isfurther described in the examples.

EXAMPLES

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. The Examples are given solelyfor purpose of illustration and are not to be construed as limitationsof the present invention, as many variations thereof are possiblewithout departing from the spirit and scope of the invention.

Acid values and hydroxyl numbers are determined by standard methods asprovided by ASTM D3339 and ASTM E-222, respectively. Acid values arereported as mg KOH per g of plasticizer and hydroxyl numbers arereported as mg KOH per g of plasticizer.

Viscosities are measured at 25° C. using a Brookfield DV-III Ultrarheometer with spindle #31 at 25%, 50%, and 75% torque, with 50% torquebeing the usual torque setting. Alternatively, depending on theviscosity of the sample, viscosities can also be measured at othertemperatures, including up to about 50° C. or higher.

Stress-Strain is evaluated using ASTM D412 and reported as tensilestrength modulus (PSI) at 100% elongation, and percent elongation.

Hardness is evaluated using ASTM D2240 and reported as Shore A Hardnessfor 15 seconds at 21° C.

Volume and surface resistivity can be determined using ASTM D257. Volumeresistivity is defined as the electrical resistance through a cube ofinsulating material. When expressed as ohm·cm (Ω·cm) this is theelectrical resistance through a one-inch cube of insulating material.Surface resistivity is defined as the electrical resistance of thesurface of an insulator material. It is measured from electrode toelectrode along the surface of the insulator sample and reported askohm/sq (kΩ/sq).

Number average molecular weights are also reported, as calculated byMiller-Macosko Theory. See, Christopher W. Macosko, Douglas R. Miller,“A new derivation of average molecular weights of nonlinear polymers”Macromolecules, 1976, 9(2), PP 199-206, which is incorporated byreference herein in its entirety.

Table 1 summarizes various properties for the polymeric plasticizercompositions of the present invention. The reported viscosity data inTable 1 was measured at 25° C. using a Brookfield DV-III Ultra rheometerwith spindle #31 at 50% torque.

Table 2 and Table 3 summarize data for properties of plasticizedpolyvinyl chloride (PVC) polymer compositions prepared, as described inExample 2, with the indicated polymeric plasticizer compositions of thepresent invention, as described in Example 1.

Example 1 General Procedure for Preparation of Polymeric PlasticizerCompositions

The polymeric plasticizer compositions are made using the followinggeneral procedures.

Procedure When the Aromatic Acid Source is an Aromatic Diacid or Esteror Anhydride

The aromatic acid source, the glycol, and the C₄-C₃₆ monocarboxylicacid, or ester or anhydride thereof are charged into a 4 neck roundbottom flask reactor and then the reactor is placed in a heating mantlethat is connected to a temperature controller. A nitrogen gas inlet, athermocouple, and a mechanical stirrer are connected to the reactor. Thereaction is performed at 189-250° C. under nitrogen sparging conditions.When proper acidity is achieved by sampling and measuring the acidvalue, the reaction is terminated and characterized.

Procedure: Aromatic Polyester or Polycarbonate as an Aromatic AcidSource

A solid polymeric thermoplastic polyester such as PET is used as theacid source, for example PET or recycled PET (rPET) pellets or flakes.The polymeric thermoplastic polyester, the glycol, or C₄-C₃₆ alcohols,and the combination of thereof, and catalyst are charged into the samereaction set up. Glycolysis is performed at 180-250° C. under nitrogensparging. When the solid polymeric material is completely digested, thereaction mixture is cooled to 100-130° C. and the C₄-C₃₆ monocarboxylicacid, or ester or anhydride, or diacid, or hydroxyacid, and combinationthereof are added. Any other components are also added at this point.The temperature controller is set at 180-250° C., and the esterificationreaction is performed under nitrogen sparging condition. Anyesterification by-product, for example water, and/or transesterificationby-product, for example methanol or other alcohols, is eliminated fromthe reaction system. The reaction is allowed to proceed until thedesired acid number is achieved.

If additional or other optional components are included, these aregenerally added at this time.

The resulting polymeric plasticizer composition is useful forplasticizing various thermoplastic polymers.

Polymer Plasticizer Compositions 1-23 of the present invention wereprepared using the general experimental procedure described in thisExample 1. The reactant components used to prepare the polymericplasticizer compositions are reported on a weight percentage basis. rPETindicates recycled PET and rPG indicates recycled propylene glycol. Forall of the following Polymeric Plasticizer Compositions the followingcatalyst was used: 500 to 1000 ppm titanium (IV) butoxide.

Polymeric Plasticizer Composition 1. 15.25% rPET, 14.95% 1,4-butanediol,14.95% 1,3-butanediol, 13.68% decanoic acid, 5.26% 12-hydroxystearicacid, 17.96% succinic acid, and 17.96% adipic.

Polymeric Plasticizer Composition 2. 15.25% rPET, 15.06% 1,4-butanediol,15.06% 1,3-butanediol, 7.22% decanoic acid, 4.00% dodecanoic acid, 5.28%12-hydroxystearic acid, 18.94% succinic acid, and 18.94% adipic acid.

Polymeric Plasticizer Composition 3. 15.28% rPET, 15.28% rPG, 6.42%1,4-butanediol, 6.42% 1,3-butanediol, 13.95% decanoic acid, 5.35%12-hydroxystearic acid, 18.65% succinic acid, and 18.65% adipic acid.

Polymeric Plasticizer Composition 4. 15.06% rPET, 16.68% rPG, 47.69%2-ethylhexanoic acid, and 20.57% dimer fatty acid.

Polymeric Plasticizer Composition 5. 12.81% rPET, 14.20%, rPG, 55.49%2-butyloctanoic acid, and 17.80% dimer fatty acid.

Polymeric Plasticizer Composition 6. 15.07% rPET, 14.61% 1,4-butanediol,14.61% 1,3-butane diol, 15.64% decanoic acid, 5.14% hydroxystearic acid,17.47% succinic acid, and 17.47% adipic acid.

Polymeric Plasticizer Composition 7. 15.49% rPET, 15.03% 1,4-butanediol,15.03% 1,3-butane diol, 11.40% decanoic acid, 5,27% 12-hydroxystearicacid, 18.90% succinic acid, and 18.90% adipic acid.

Polymeric Plasticizer Composition 8. 15.27% rPET, 15.28% rPG, 6.11%1,4-butanediol, 6.11% 1,3-butanediol, 15.64% decanoic acid, 5.09%12-hydroxystearic acid, 18.25% succinic acid, and 18.25% adipic acid.

Polymeric Plasticizer Composition 9. 20.00% rPET, 15.00% rPG, 5.20%1,4-butanediol, 5.20% 1,3-butanediol, 16.06% decanoic acid, 5.35%12-hydroxystearic acid, 16.60% succinic acid, and 16.60% adipic acid.

Polymeric Plasticizer Composition 10. 16.65% rPET, 18.47% rPG, 16.73%decanoic acid, 33.60% dimer fatty acid, and 14.55% succinic acid.

Polymeric Plasticizer Composition 11. 20.39% rPET, 4.37% rPG, 8.12%glycerol, 5.18% 1,3-butanediol, 41.48% decanoic acid, 5.28% rincinoleicacid, 6,78% succinic acid, and 8.40% adipic acid.

Polymeric Plasticizer Composition 12. 18.41% rPET, 18.41% rPG, 26.13%decanoic acid, 4.60% dimer fatty acid, and 25.90% succinic acid.

Polymeric Plasticizer Composition 13. 29.02% rPET, 10.41% rPG, 5.30%glycerol, 4.06% 1,3-butanediol, 29.74% dodecanoic acid, and 21.47%succinic acid.

Polymeric Plasticizer Composition 14. 18.84% rPET, 7.28% rPG, 8.06%glycerol, 2.87% 1,3-butanediol, 47.88% dodecanoic acid, and 15.07%succinic acid.

Polymeric Plasticizer Composition 15. 13.54% rPET, 15.04% rPG, 52.92%neodecanoic acid, and 18.51% dimer fatty acid.

Polymeric Plasticizer Composition 16. 16.37% rPET, 18.17% rPG, 43.08%levulinic acid, and 22.38% dimer fatty acid.

Polymeric Plasticizer Composition 17. 8.45% rPET, 10.45% rPG, 78.59%decyltetradecanoic acid, and 12.84% dimer fatty acid.

Polymeric Plasticizer Composition 18. 23.00% rPET, 20.50% rPG, 22.5%succinic acid, 24.00% decanoic acid, and 10.00% ethyl levulinateglycerol ketal.

Polymeric Plasticizer Composition 19. 23.00% rPET, 21.50% rPG, 24.50%succinic acid, 24.00% decanoic acid, and 7.00% polycarbonate polyol(Mn=1000 g/mol).

Polymeric Plasticizer Composition 20. 23.00% rPET, 21.50% rPG, 24.50%succinic acid, 24.00% decanoic acid, and 7.00% poly(bisphenol-Acarbonate).

Polymeric Plasticizer Composition 21. 16.20% rPET, 16.20% rPG, 14.58%succinic acid, and 52.02% methyl oleate.

Polymeric Plasticizer Composition 22. 18.51% rPET, 9.51% rPG, 4.34%neopentyl glycol, 7.92% glycerin, 19.69% succinic acid, and 40.03%decanoic acid.

Polymeric Plasticizer Composition 23. 20.49% rPET, 20.49% rPG, 5.69%neopentyl glycol, 28.07% succinic acid, and 25.26% decanoic acid.

Example 2 Plasticized Polyvinyl Chloride Polymer Compositions

Using standard manufacturing techniques, plasticized polymericcompositions are made using the polymeric plasticizer compositions ofthe present invention and the desired polymer, for example athermoplastic polymer.

The plasticized polymers can be used for example as a replacement forrubber, and have applications in areas including electrical cableinsulation, flooring, coatings, tubing, inflatable products, andimitation leather.

The following formulation is an example of a plasticized polymercomposition useful for wire and cable coatings.

Plasticized Polymer Formulation For Wire and Cable Applications

Polyvinylchloride (PVC) resin: 100 PHR

Polymeric Plasticizer of the Present Invention: 35 PHR

Additional Low Molecular Weight Plasticizers: 30 PHR

Ca/Zn: 4.5 PHR

Stearic acid: 0.2 PHR

Calcined Clay: 12 PHR

Antimony Oxide: 3 PHR

In the above formulation, PHR refers to parts per hundred parts ofresin, which is a standard means in the art for referring to polymerformulations. In this example a PVC resin is used corresponding to 100parts. The remaining components are with reference to the 100 partstotal of the PVC resin. Three different plasticized polymer compositionswere prepared using 35 PHR of the indicated polymeric plasticizercompositions. The resulting plasticized PVC is useful for wire and cableapplications.

Composition A. Plasticized Polyvinylchloride (PVC)—Control Composition

This composition was prepared according to the above formula of Example2 using 35 PHR of a commercially available polymeric plasticizer(control composition).

Composition B. Plasticized Polyvinylchloride (PVC)

This composition was prepared according to the above formula of Example2 using 35 PHR of Polymeric Plasticizer Composition 1 described inExample 1.

Composition C. Plasticized Polyvinylchloride (PVC)

This composition was prepared according to the above formula of Example2 using 35 PHR of Polymeric Plasticizer Composition 2 described inExample 1.

Composition D. Plasticized Polyvinylchloride (PVC)

This composition was prepared according to the above formula of Example2 using 35 PHR of Polymeric Plasticizer Composition 22 described inExample 1.

Composition E. Plasticized Polyvinylchloride (PVC)

This composition was prepared according to the above formula of Example2 using 35 PHR of Polymeric Plasticizer Composition 23 described inExample 1.

The following properties were determined on the plasticized polymericplasticizer compositions: Stress-Strain was evaluated using ASTM D412and reported as tensile strength (PSI) and modulus at 100% elongation.Furthermore, the stress strain, reported as tensile strength and modulusat 100% elongation was measured on samples aged at 136° C. for 7 daysand on samples aged in oil at 60° C. for 7 days (UL 1581). The oil usedwas petroleum oil, CAS 64742-52-5, available from Sunoco under the tradename IRM 902. Hardness was evaluated using ASTM D2240 and reported asShore A Hardness for 15 seconds at 21° C. and percent elongation atbreak. Volume and surface resistivity were determined using ASTM D257.Volume resistivity is defined as the electrical resistance through acube of insulating material. When expressed as ohm·cm (Ω·cm), this isthe electrical resistance through a one-inch cube of insulatingmaterial. Surface resistivity is defined as the electrical resistance ofthe surface of an insulator material. It is measured from electrode toelectrode along the surface of the insulator sample and reported askohm/sq (kΩ/sq).

Also, brittleness and limiting oxygen index were determined. Brittlenessis measured by ASTM D746 and reported as ° C. The limiting oxygen index(LOI) is the minimum concentration of oxygen, expressed as a percentage,that will support combustion of a polymer. It is measured by passing amixture of oxygen and nitrogen over a burning specimen, and reducing theoxygen level until a critical level is reached. LOI values for differentplastics are determined by standardized tests, such as the ISO 4589 andASTM D2863.

Table 2 and Table 3 summarize these properties of the plasticizedthermoplastic polymer Compositions A, B, C, D, and E.

Example 3 Plasticized Polyethylene Terephthalate (PET) Composition

PET pellets and Polymeric Plasticizer Composition 6 described in Example1, 100 grams of each, were charged into a 500 mL 4-neck round bottomflask. The mixture was placed under a nitrogen atmosphere and stirredslowly with heating, at a temperature of 220° C., until the pelletscompletely dissolved. The temperature of the reaction mixture was cooledto 200° C. and poured into Teflon dishes to form an opaque, tanmaterial.

TABLE 1 Polymeric Plasticizer Composition Properties PolymericPlasticizer Hydroxyl Number Average Composition Acid Value NumberViscosity Molecular Weight No. (mg KOH/g) (mg KOH/g) (cP) (grams/mole) 10.4 25.1 7648 1500 2 0.5 21.5 16,203 2000 3 2.0 31.9 19,316 1500 4 1.819.6 221 500 5 2.5 17.1 282 600 6 1.6 12.5 5849 1500 7 0.7 19.2 11,6982000 8 2.3 5.0 10,626 1500 9 1.7 16.4 15,731 1500 10 0.6 14.7 17,4031500 11 1.7 5.0 1810 1000 12 0.5 26.5 4174 1000 13 1.2 13.1 73,784 150014 3.9 11.4 2852 1000 15 1.3 15.0 811 600 16 1.2 38.9 6494 500 17 1.67.0 348 900 18 0.5 51.2 8892 650 19 0.9 36.2 5099 940 20 1.9 30.9 33,1261000 21 1.1 3.6 420 1000 22 2.0 10.0 4800 1000 23 1.7 5.8 12,000 1000

TABLE 2 Plasticized Polymer Composition Properties Modulus PlasticizedTensile at Percent Volume Surface Polymer Strength 100% HardnessElongation Resistivity Resistivity Composition No. (PSI) ElongationShore A at Break (Ω · cm) (kΩ/sq.) A 2912 1253 77.3 420 2.80 × 10¹⁴ 1.60× 10¹⁵ B 3121 1532 81.0 422 4.64 × 10¹⁴ 1.45 × 10¹⁵ C 3095 1600 82.0 4175.29 × 10¹⁴ 2.68 × 10¹⁵ D 2915 1671 86.0 365  1.4 × 10¹⁵  2.7 × 10¹⁵ E3130 1791 85.5 375  1.8 × 10¹⁵  2.2 × 10¹⁵

TABLE 3 Plasticized Polymer Composition Properties Aging at 136° C.Aging at 60° C Plasticized for 7 days Oil for 7 days Polymer % %Limiting Compo- Tensile Elon- Tensile Elon- Brittle- Oxygen sitionStrength gation Strength gation ness Index No. (PSI) at Break (PSI) atBreak ° C. (LOI) A 2870 404 2905 361 −22.0 26.9 B 2923 369 2861 335−18.0 27.3 C 2724 390 2766 334 −15.0 27.3 D 2887 345 2858 327 −16.0 28.3E 2923 304 2970 328 −12.5 27.5

Incorporation by Reference

The entire disclosure of each of the patent documents, includingcertificates of correction, patent application documents, scientificarticles, governmental reports, websites, and other references referredto herein is incorporated by reference herein in its entirety for allpurposes. In case of a conflict in terminology, the presentspecification controls.

Equivalents

The invention can be embodied in other specific forms without departingfrom the spirit or essential characteristics thereof. The foregoingembodiments are to be considered in all respects illustrative ratherthan limiting on the invention described herein. In the variousembodiments of the methods and systems of the present invention, wherethe term comprises is used with respect to the recited steps orcomponents, it is also contemplated that the methods and systems consistessentially of, or consist of, the recited steps or components. Further,it should be understood that the order of steps or order for performingcertain actions is immaterial so long as the invention remains operable.Moreover, two or more steps or actions can be conducted simultaneously.

In the specification, the singular forms also include the plural forms,unless the context clearly dictates otherwise. Unless defined otherwise,all technical and scientific terms used herein have the same meaning ascommonly understood by one of ordinary skill in the art to which thisinvention belongs. In the case of conflict, the present specificationwill control.

In some instances the required and addition components describe hereincan be categorized differently or in more than one category.

All percentages and ratios used herein, unless otherwise indicated, areby weight. Also, throughout the disclosure the term “weight” is used. Itis recognized the mass of an object is often referred to as its weightin everyday usage and for most common scientific purposes, but that masstechnically refers to the amount of matter of an object, whereas weightrefers to the force experienced by an object due to gravity. Also, incommon usage the “weight” (mass) of an object is what one determineswhen one “weighs” (masses) an object on a scale or balance.

1. A polymeric plasticizer composition comprising a reaction product of:(a) an aromatic acid source selected from an aromatic diacid, anaromatic diacid anhydride, an aromatic diacid monoester, an aromaticdiacid diester, an aromatic linear ester oligomer, an aromatic linearthermoplastic polyester, and combinations thereof; (b) a glycol; and (c)a C₄-C₃₆ monocarboxylic acid, or ester or anhydride thereof.
 2. Apolymeric plasticizer composition according to claim 1 having a numberaverage molecular weight from 500 to 25,000 grams/mole. 3.-4. (canceled)5. A polymeric plasticizer composition according to claim 1 having anacid value less than 10 mg KOH/g. 6.-7. (canceled)
 8. A polymericplasticizer composition according to claim 1 having a hydroxyl numberless than 80 mg KOH/g. 9.-11. (canceled)
 12. A polymeric plasticizercomposition according to claim 1 having a polymer backbone ether valueless than about 5 percent by weight ether oxygen based on the weight ofthe polymeric plasticizer composition.
 13. A polymeric plasticizercomposition according to claim 1 wherein the aromatic acid source is anaromatic linear thermoplastic polyester.
 14. A polymeric plasticizercomposition according to claim 13 wherein the aromatic linearthermoplastic polyester is selected from polyethylene terephthalate,polybutylene terephthalate, polytrimethylene terephthalate, polyethylenefuranoate, glycol-modified polyethylene terephthalate, copolymers ofterephthalic acid and 1,4-cyclohexanedimethanol, isophthalicacid-modified copolymers of terephthalic acid and1,4-cyclohexanedimethanol, copolymers of 2,5-furandicarboxylic acid anda glycol, copolymers of dialkyl 2,5-furandicarboxylate and a glycol,dihydroferulic acid polymers, copolymers of2,2,4,4-tetramethyl-1,3-cyclobutanediol with isophthalic acid,terephthalic acid or orthophthalic derivatives, and combinationsthereof.
 15. (canceled)
 16. A polymeric plasticizer compositionaccording to claim 1 further comprising a thermoplastic polycarbonate, athermoplastic polycarbonate blend with a thermoplastic polyester, athermoplastic polycarbonate transreaction product with a thermoplasticpolyester, and combinations thereof.
 17. A polymeric plasticizercomposition according to claim 1 further comprising poly(bisphenol-Acarbonate), a blend or transreaction product of poly(bisphenol-Acarbonate) and polyethylene terephthalate, a blend or transreactionproduct of poly(bisphenol-A carbonate) and polybutylene terephthalate,and combinations thereof.
 18. A polymeric plasticizer compositionaccording to claim 1 wherein the glycol is selected from ethyleneglycol, propylene glycol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol,1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol,1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol,2-methyl-1,3-propanediol, neopentyl glycol, glycerol,trimethylolpropane, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol,1,3-cyclohexanedimethanol, diethylene glycol, tetraethylene glycol,dipropylene glycol, triethylene glycol, tripropylene glycol,polyethylene glycol, polypropylene glycol, polycarbonate polyols,pentaerythritol, sorbitol, and block or random copolymer glycols ofethylene oxide and propylene oxide, aliphatic polyester polyols,2,2,4,4-tetramethyl-1,3-cyclobutanediol, and combinations thereof.19.-20. (canceled)
 21. A polymeric plasticizer composition according toclaim 1 wherein the C₄-C₃₆ monocarboxylic acid is selected from benzoicacid, phenylacetic acid, levulinic acid, naphthenic acid, norbornenecarboxylic acid, 2-furoic acid, decanoic acid, undecanoic acid,dodecanoic acid, tridecanoic acid, tetradecanoic acid, neodecanoic acid,2-butyloctanoic acid, 2-ethylhexanoic acid, and combinations thereof.22.-23. (canceled)
 24. A polymeric plasticizer composition according toclaim 1 wherein the C₄-C₃₆ monocarboxylic acid ester is a C₁-C₇ alcoholester of a C₄-C₃₆ monocarboxylic acid. 25.-26. (canceled)
 27. Apolymeric plasticizer composition according to claim 1 furthercomprising a C₄-C₃₆ alcohol.
 28. A polymeric plasticizer compositionaccording to claim 27 wherein the C₄-C₃₆ alcohol is selected fromnorborneol, alkoxylates of branched or linear alkyl phenols, branched orlinear saturated or unsaturated alkyl alcohols, alkoxylated branched orlinear saturated or unsaturated alkyl alcohols, 2-phenoxy ethanol,2-phenoxy propanol, benzyl alcohol, furfuryl alcohol, alkoxylatedfurfuryl alcohol, 2-(hydroxymethyl)tetrahydrofuran,6,6-dimethyl-2-norpinen-2-ethanol, and alkoxylated6,6-dimethyl-2-norpinen-2-ethanol, cyclohexanol, alkoxylatedcyclohexanol, 2-cyclohexylethanol, alkoxylated 2-cyclohexyl ethanol,2-cyclohexyloxyethanol, 1-ethynyl-1-cyclohexanol, 2-phenylethanol,alkoxylated 2-phenyl ethanol, alkoxylated phenols, alkoxylatednorborneol, farnesol, hydrogenated farnesol, geraniol, hydrogenatedgeraniol, and combinations thereof.
 29. A polymeric plasticizercomposition according to claim 1 further comprising a C₃-C₃₆ saturatedor unsaturated aliphatic linear, branched, or cyclic polyacid orhydroxyl substituted polyacid, or esters or anhydrides thereof, ancombinations thereof.
 30. A polymeric plasticizer composition accordingto claim 29 wherein the C₃-C₃₆ saturated or unsaturated aliphaticlinear, branched, or cyclic polyacid or hydroxyl substituted polyacid,or esters or anhydrides thereof, and combinations thereof, wherein theforegoing polyacid is a diacid. 31.-32. (canceled)
 33. A polymericplasticizer composition according to claim 1 further comprising ahydroxyl substituted C₃-C₃₆ monocarboxylic acid, or ester or anhydridethereof, and combinations thereof.
 34. A polymeric plasticizercomposition according to claim 33 wherein the hydroxyl substitutedC₃-C₃₆ monocarboxylic acid, or ester or anhydride thereof is selectedfrom 12-hydroxy stearic acid, ricinoleic acid, an alkyl levulinate triolketal, lactic acid, and combinations thereof. 35.-36. (canceled)
 37. Apolymeric plasticizer composition according to claim 1 furthercomprising an aromatic triacid or aromatic tetraacid, or esters oranhydrides thereof, and combinations thereof; wherein at least one ormore of the following (a), (b), or (c) apply to the polymericplasticizer composition: (a) the polymeric plasticizer composition hasan acid value of less than 5 mg KOH/g, (b) the C₄-C₃₆ alcohol is not aC₈-C₁₂ alcohol, or (c) the C₄-C₃₆ monocarboxylic acid, or ester oranhydride thereof is not a C₁₂-C₁₈ monocarboxylic acid.
 38. A polymericplasticizer composition according to claim 1 further comprising ahydrophobe.
 39. A polymeric plasticizer composition according to claim38 wherein the hydrophobe is selected from ricinoleic acid, castor oil,ethoxylated castor oil, vegetable oils, fatty acids, fatty acid esters,modified vegetable oils, fatty triglycerides, cardanol-derived products,recycled cooking oil, hydroxy-functional materials derived fromepoxidized, ozonized, or hydroformylated fatty esters or fatty acids,alkoxylated alkyl phenols, alkoxylated fatty alcohols, and combinationsthereof.
 40. A polymeric plasticizer composition according to claim 1,wherein one or more of the following apply: (a) the weight ratio ofaromatic acid source in the polymeric plasticizer composition is from 5to 90 weight percent, (b) the weight ratio of glycol in the polymericplasticizer composition is from 5 to 70 weight percent, or (c) theweight ratio of the C₄-C₃₆ monocarboxylic acid, or ester or anhydridethereof is from 5 to 80 weight percent.
 41. A polymeric plasticizercomposition according to claim 1 having a recycle content as definedherein greater than 10 weight percent. 42.-44. (canceled)
 45. Aplasticized thermoplastic polymer composition comprising (a) from 10% to80% by weight percent of a polymeric plasticizer composition; and (b)from 20% to 90% by weight of a thermoplastic polymer, wherein saidpolymeric plasticizer composition comprises a reaction product of: (i)an aromatic acid source selected from an aromatic diacid, an aromaticdiacid anhydride, an aromatic diacid monoester, an aromatic diaciddiester, an aromatic linear ester oligomer, an aromatic linearthermoplastic polyester, and combinations thereof; (ii) a glycol; andiii a C₄-C₃₆ monocarboxlic acid, or ester or anhydride thereof.
 46. Acomposition according to claim 45 wherein the thermoplastic polymer isselected from polyvinyl chloride, polyethylene terephthalate, nitrilebutyl rubber, acrylonitrile-butadiene rubber, polyvinyl chloridepolyvinyl alcohol copolymers, acrylates, natural & synthetic rubber,cellulose acetate butyrate, cellulose nitrate, ethyl cellulose,polyvinyl butyral, chlorinated rubber, polyisoprene, styrene butadienecopolymers, butadiene, halobutyl rubber and combinations thereof.
 47. Acomposition according to claim 46 wherein the thermoplastic polymer ispolyvinyl chloride. 48.-49. (canceled)
 50. A process for preparing apolymeric plasticizer composition comprising reacting: (a) an aromaticacid source selected from an aromatic diacid, an aromatic diacidanhydride, an aromatic diacid monoester, an aromatic diacid diester, anaromatic linear ester oligomer, an aromatic linear thermoplasticpolyester, and combinations thereof; (b) a glycol; and (c) a C₄-C₃₆monocarboxylic acid, or ester or anhydride thereof at a temperaturebetween 80° C. and 260° C.
 51. A process for preparing a polymericplasticizer composition according to claim 50 further comprisingperforming the reaction in the presence a catalyst. 52.-58. (canceled)59. A method of plasticizing a thermoplastic polymeric materialcomprising, combining: (a) from 10% to 80% by weight percent of apolymeric plasticizer composition according; and (b) from 20% to 90% byweight of a thermoplastic polymer, wherein said polymeric plasticizercomposition comprises a reaction product of: (i) an aromatic acid sourceselected from an aromatic diacid, an aromatic diacid anhydride, anaromatic diacid monoester, an aromatic diacid diester, an aromaticlinear ester oligomer, an aromatic linear thermoplastic polyester, andcombinations thereof; (ii) a glycol; and (iii) a C₄-C₃₆ monocarboxylicacid, or ester or anhydride thereof.
 60. A method according to claim 59wherein the thermoplastic polymeric material is selected from polyvinylchloride, polyethylene terephthalate, nitrile butyl rubber,acrylonitrile-butadiene rubber, polyvinyl chloride polyvinyl alcoholcopolymers, acrylates, natural & synthetic rubber, cellulose acetatebutyrate, cellulose nitrate, ethyl cellulose, polyvinyl butyral,chlorinated rubber, polyisoprene, styrene butadiene copolymers,butadiene, halobutyl rubber and combinations thereof.
 61. (canceled)